Process for the dimensional control of cellulose textile materials by applying polymeric acetals and products resulting therefrom



United States Patent PROCESS FOR THE DIMENSIONAL CONTROL OF CELLULOSE TEXTILE MATERIALS BY APPLY- ING POLYIVIERIC ACETALS' AND PRODUCTS RESULTING THEREFROM Bernard H. Kres s, Ambler, Pa., assignor to Quaker Chemical Products Corporation, Conshohocken, Pa., a corporation of Pennsylvania No Drawing. Application January 8, 1954, Serial No. 403,057

11 Claims. (Cl. 8--116) This invention relates to the application of certain acetal condensation products to cellulosic fabrics, yarns or fibers, such as rayon and cotton, in order to obtain dimensional control or stabilization of the fabric, yarn or fiber against progressive, dimensional shrinkage under repeated washings.

A considerable body of both theoretical and practical literature has been built up around the use of formaldehyde and polymers thereof in order to limit shrinkage and dimensional control of cellulosic fibers. Dimensional control has been usually obtained at the expense of fabric strength, i. e. considerable tendering accompanies such treatment.

The use of formalin solution has never been widely accepted because of the difficulty of adequate control of the procedure and the volatility of the formaldehyde. This factor alone militates against wide use because irritating and harmful vapors are present and released during the entire process and considerable loss of formaldehyde content occurs.

It is well known in the art to treat cellulosic materials, for purposes of dimensional control, to stabilize same against progressive dimensional shrinkage under repeated washings, with water-soluble urea or melamine formaldehyde condensates in the presence of acidic or potentially acidic catalysts. It is also well known to apply free aldehydes, such as formaldehyde and glyoxal, to cellulosic materials in the presence of acidic catalysts in order to achieve dimensional control.

It is a well-known and Well-recognized fact that the urea and melamine condensates possess inherent disadvantages which limit their field of usefulness. For example, some of these products emit objectionable odors during their application to textile materials and in certain cases these odors may persist in the finished fabric. In other'instances objectionable odors may develop in the fabric after finishing. Some of these condensates bring about considerable tendering and embrittlement of the fibers, thereby lowering the fabric tensile strength. These condensates also possess the unfortunate property of retaining chlorine. Thus fabric treated with these condensates and subsequently bleached during laundering with chlorine-containing bleaches, will retain this chlorine and release it as hydrochloric acid when the fabric is ironed. This hydrochloric acid seriously tenders the fabric to the extent that these urea and melamine formaldehyde condensates cannot be applied to white or pastel shades which may be bleached during laundering. Furthermore, it has been observed that the degree of durability to laundering obtained through the use of these condensates is rather limited.

It is also well known in the art to use combinations of either water-soluble cellulosic polymers or polyvinyl alcohol with formalin to achieve dimensional control. This same drawbacks in the use of formalin applyto these processes. The present invention overcomes the foregoing difiiculties by providing aprocess in which no Objection- EXAMPLE 1 Diethylene glycol ..moles- 1 Paraformaldehyde do 1 Sulfuric acid. do 0,001 Toluene ml 25 The above components are mixed and heated under reflux in an apparatus equipped with a water trap. The solution is refluxed and water removed by azeotropic distillation. When 1 mole of water of reaction is removed the desired reaction is complete. The reaction mixture is neutralized withdilute sodium hydroxide solution and toluene is removed by evaporation in vacuo'at temperatures not exceeding C. The product is a viscous liquid, setting to a crystalline mass below 16 'C. It's completely water-soluble and also soluble' in toluene and esters. The product has a molecular weight of 480 (Rast) and a hydroxyl equivalent of 220 which indicates it has a linear polymeric structure. It has a specific gravity of 1.155 at 94 F. The refractive index'is Polymeric condensation products may also be made starting with ethylene glycol, a propylene glycol, a butylene glycol, dipropylene glycol, dibutylene glycols and higher dialkylene glycols, polyalkylene glycols, mixtures thereof, or their mixtures with diethylene glycol which are reactive with formaldehyde or other aldehydes'to form Water-soluble products or products which are dispersible in Water, either alone or with the aid of appropriate adjuvants. Polyalkylene glycols, such as triethylene glycol, tetraethylene glycol, tripropylene glycol and the like may also be used, eithr alone or in admixture with the aforementioned "glycols. Likewise polyols, such as glycerine, pentaerythritol and sorbitol, may be added to the alkylene glycols in amounts up to about 50 mol. percent of the glycols for reaction with the aldehyde for forming water-soluble or Water-dispersible products. Instead .of the paraformaldehyde of the above example, trioxane, methylal, aqueous formalin and similar formaldeyde-generating compounds may be used. Instead of formaldehyde, otherreactive aldehydes, such as acetaldehyde, propanal, butanal, benzaldehyde, glyoxal, terephthalaldehyde and other dialdehydes, may be used, containing not more than 8 carbon atoms in the monomeric form, and mixtures thereof; in forming watersoluble or water-dispersible condensation products with the alkylene glycols. The term alkylene" is understood to include a doubly unsatisfied aliphatic radical containing a substituted or unsubstituted straight chain possessing from two to four carbon atoms in the chain and having its unsatisfied valences on either adjacent or separated carbon atoms.

I prefer to react substantially equimolar ratios of the aldehyde to the glycol in making my condensation products, but I may also use an excess of either reactant. In forming the condensation products, it is necessary to have a strongly acidic catalyst present, such as sulfuric acid, alkane sulfonic acids, phosphoric acids, and acid halides, such as zinc chloride, stannic chloride, aluminum chloride, acid clays, etc. In general, those catalysts Wellknown in the art for alkylation, esterification and Friedei- Crafts condensation reactions may be employed in making the condensation products. The condensation products of this invention are of polymeric nature, as illustrated by the molecular weight of the product of Example 1. By polymeric, I mean that my condensation products contain two or more aldehyde units and two or more polyhydric alcohol units per molecule of condensation product. g

It is preferred to have toluene present as an azeotropic liquid medium which does not interfere with the reaction. Other azeotropic vehicles which may be used are benzene, xylene, ethyl benzene, and the like.

Products, such as the one described in Example 1, have been found to be of value in the dimensional control of rayon and cotton fabrics without serious loss of tensile strength. The general application of these polymeric acetals involves padding cellulosic fabric through aqueous solutions or dispersions of the polymeric acetals containing from 0.5 to 25% by weight of the acetal. The padding bath must contain, in addition to the acetal, some acidic-type catalyst, such as aluminum chloride, stannic chloride, aluminum sulfate, oxalic acid, zinc chloride, sodium acid sulfate, sodium or potassium alum, dimethyl oxalate, ammonium chloride, etc., in amount of about 5% to about 200% by weight of the acetal content. The treated fabric may then be dried at an appropriate temperature and subsequently cured at a temperature of at least 250 F. for about /2 to minutes. The time of cure varies inversely with the temperature. The cured fabric may then be washed lightly with a detergent and a mild alkali, rinsed thoroughly and dried in a relaxed state. Fabrics so treated with these acetals will not on dergo progressive shrinkage even when laundered in boiling soap solution as in American Association of Textile Chemists and Colorists (A. A. T. C. C.) 1952 Standard Test Method 14-52 for cotton and linen fabrics.

EXAMPLE 2 A padding solution is made up as follows:

4.5% condensation product described in Example 1. 2.0% aluminum sulfate-hydrated 9 3.5% water A light-weight rayon gabardine shirting material which had been bleached and scoured was marked with a San forize Test Marker. The fabric was then passed through the padding solution and rolls twice. The padder was adjusted for 100% wet pick-up. The fabric was then placed on a frame so as to hold it to the dimensions it possessed before impregnation and dried in a hot air oven at 180 F. The fabric was then cured at temperatures of 300 F. for 5 minutes. The following results were obtained:

The tests used are as follows:

Wash test-A. A. T. C. C. 1952 Standard Test Method Tensile strength-Federal Spec. CCCT-191B Method 51022" Width Tear strengthibid., Method 5132 Crease recoveryA. A. T. C. C., 1952, p. 155, Monsanto testertentative 66-52 Chlorine retentionA. A. T. C. C., p. 88 (1952), tentative It may thus be seen that a non-chlorine retentive dimensional control agent has been applied which yields no serious loss of tensile and tear strength and with significant increase in crease recovery.

The exact chemical reaction with the cellulose is not known but the retention of formaldehyde is permanent in that 5 standard washes do not significantly remove it.

A procedure for the determination of formaldehyde in fabric has been modified as follows:

Fabric (10 grams) was boiled with 20% sulfuric acid. The distillate was trapped in distilled water. This then was mixed with a molar solution of sodium sulfite and the formaldehyde determined by titration of released base.

The results on rayon gabardine are as follows:

Table I Percent 0011- Percent Formdensation Percent Warp aldehyde Re- Product of Shrinkage, 1 covered from Example 1 in Wash Fabric treatment bath The retention of formaldehyde content on the fabric is shown below:

Table II Percent Condensation Percent Form- Percent Form Product of aldehyde light aldehyde 5 Example 1 in hand washed Washes Treatment fabric Bath Various acidic and potentially acidic catalysts are applicable in using my process for dimensional control. This is demonstrated in the following example:

EXAMPLE 3 In all cases treatment was similar to that described in The product has been found applicable to various weaves and combinations of rayon, as well as cotton. The following examples will serve to indicate the utility of the process.

. The following Examples 4 to 8 show results obtained by treating the specified textile materials as in Example 2 except where concentrations of the condensation product and catalyst are otherwise shown.

6 EXAMPLE 4- Additional'examples of acetal condensation products a which are suitable for use in my process are made as Rayon .challzs follows; l

' EXAMPLE Percent Percent I I 5 s 1 ii or 1 t sii iiiir si iii Pam i ren i 1 3,313 a al (lbs m y e g y 85 as inlEii- I as Dipropylene glycol v 7 9??? Paraformaldehyde 91% 33 Toluene I 20 Tffff ff 5? Sulfuric acid 99% 0.1 atfntrated 'T 0 These reactants were treated as in Example 1. The a resulting product was a viscous liquid which formed EXAMPLE 5 a crystalline mass below 0 C. The product was soluble Viscose rayon Shantung skirting in water or toluene and had a faint ethereal odor.

,.- I P I tW E I PLE 11 ercen BT09!) arp C d Shrinkage Sample Ps gitiioit Catalyst II Diethylene glycol I I I I 80 m Sorbitol-crystalline 32 1 h 5 3.21 31%; was washes Paraformaldehyde 91% 30 Toluene I 'Treatedasin Example 2.4 0268-81? acid 2.6 2.2 Eulfuric acid (99%) .1 ntreated.-- i 0' 10-7 These reactants were treated as in Example 1. Th

product was a crystalline mass at room temperature, EXAMPLE 6' soluble in toluene and in water, and with virtually no The fabric was a 98% rayon and 2% acetate blend. EXAMPLE 12 i i i v i a Parts s iiiiii ka z Diethylene glyc0l 106 Sample Paraformaldehyde (91%) 52 lwash 5washes Glyoxal (30%) 39 Toluene I 20 TreatedasinExample2 0.2 1.8 Sulfuric acid (99%) 0.1 Untreated 4. 6 7. 8

l These compounds were reacted as in Example 1. The product was a somewhat viscous yellow liquid with a EXAMPLE 7 faint ethereal odor. The product was soluble in water The fabric was a,50% rayon and 50% acetate blend. and in toluelm The following 'results were obtained on lightweight fiifi gg 40 shirting gabardine with equal weights of the various Sample acetalcondensation product described above (4.5%) and lwash Washes sodium sulfate-bisulfate (1 to 4) catalyst (3.0%).

EXAMPLE 13 Treated as in Example 2; 1. 53- 0. 9 Untynafed 3.9 4.6 I Percent Warp Shrinkage I 8 Composition I Cotton sheeting (80 x 80) 1 a 5 Washes p I w T "1 Examplel 3.0 3.5 ia aaaasiia 2-2 sample gg Example 12:: 2Z6 3Z1 Wash 5Washes Water alone 10.0 15.0

Treated asinExample 2n; ;;L 2.6 3.3 36 55 If desired, the polymeric chains of the compounds of Untreated 4L5 my invention may be terminated, either in whole or in part, by means of an alkyl radical possessing not more efiects due to chlorme by the afore' than 8 carbon atoms. The alkyl radical may be intromentioned standard test were observed in these samples. duced in any suitable manner I may for example, The necefsslty for Presence an and catalyst m react an aldehyde and a glycol in the presence of a minor order to gain dimensional control 1n the process is shown amount of a half ether of a glycol to Serve as a chain in the followlng example for viscose shlrtmg gabardme. stopperI Such a preparation is illustrated in the follow EXAMPLE 9 ing example:

EXAMPLE 14 P t s 11 r Parts in a e Product Used Pgdii ct Catalyst,percent r g Dlethylene glycol- 101 W h 5w h Beta methoxyethanoi 4 1 as as es Paraformaldehyde (91%) 30 d l a 0 0 N 9 2 11 e Toluene 20 giggfiti 1 III Sulfuric acid (90%) 0.1 D8: 810 9:6 114 The above materials were reacted as in Example 1 to 38"- g gflffff z 5:? yield a viscous liquid possessing a faint ethereal odor vDou'. 5.8 Sodium Alum 2.9 3.5 andsoluble in water. Its polymeric nature was shown None gf M us by Rast molecular weight determination which had a value of 637. This material was applied to a lightweight rayon gabardine shirting as in Example 2 using an aque- .ous solution containing 4.5% of this condensation product and a catalyst control consisting of 2.4% of sodium bisulfatc and 0.6% of sodium sulfate. After one light hand wash the treated sample showed a warp-wise shrinkage of 3.7% as contrasted with a shrinkage of 8.5% for the'original untreated shirting material washed under the same conditions.

The term cellulose textile material is intended to include cellulose filaments and fibers, staple or yarns, Whether in finished stages or at some intermediate stage in the production thereof, of the group consisting of natural cellulose, regenerated cellulose, such as viscose rayon, cuprammonium rayon and hydrolyzed cellulose acetate, and mixtures thereof with other natural and synthetic fibers, such as cellulose acetate, nylon, wool, etc. The term also includes fabrics, Whether knitted, woven or felted, as well as garments or other articles made from such fabrics.

1. The process of treating a cellulose textile material which comprises applying to a cellulose textile material an aqueousjbath containing an acidic catalyst and a polymeric acetal condensation product of a glycol selected from the group consisting of monoalkylene and polalkylene glycols in which the alkylene radical has 2 to 4 carbon atoms in a straight chain and mixtures of the aforesaid glycols, and a reactive aldehyde selected from the group consisting of aliphatic and carbocyclic aldehydes containing not more than 8 carbon atoms in monomeric form and mixtures of the aforesaid aldehydes, said condensation product containing at least 2 aldehyde units and at least 2 polyhydric alcohol units per molecule of condensation product, said catalyst being present in amount from about 5% to about 200% by Weight of the said polymeric condensation product, said polymeric condensation product being present in said bath in amount from about 0.5% to about 25% by weight of the bath and heating the treated textile material at an elevated temperature until the cellulose and said polymeric condensation product react and dimensionally stabilize the cellulose material to laundering.

2. The process of treating a cellulose textile material which comprises applying to a cellulose textile material an aqueous bath containing'an acidic catalyst and a polymeric acetal condensation product of a glycol select ed from the group consisting of monoalkylene and polyalkylene glycols in which the alkylene radical has 2 to 4 carbon atoms in a straight chain and mixtures of the aforesaid glycols, and a reactive aldehyde selected from the group consisting of aliphatic and carbocyclic aldehydes containing not more than 8 carbon atoms in monomeric form and mixtures of the aforesaid aldehydes, said condensation product containing at least 2 aldehyde units and at least 2 polyhydric alcohol units per molecule of condensation product,- said catalyst being present in amount from about 5% to about 200% by weight of the said polymeric condensation product, said polymeric con densation product being present in said bath'in amount from about 0.5% to about 25 by Weight of the bath and heating the treated textile material to a temperature of at least about 250 F. for about /2 to about 10 minutes until the cellulose and said polymeric condensation product react and dimensionally stabilize the cellulose material to laundering.

3. The process of treating a cellulose textile material as defined in claim 1 wherein the bath contains a polymeric condensation product of diethylene glycol and formaldehyde.

4. The process of treating a cellulose textile material as defined in claim 1 wherein the polymeric acetal condensation product in the bath is a polymeric condensation product of a glycol selected from the group consisting of monoalkylene and dialkylene glycols in which the alkylene radical has 2 to 4 carbon atoms, an aliphatic polyhydric alcohol containing from 3 to 6 hydroxyl groups and from 3 to 6 carbon atoms, and a reactive aldehyde selected from the group consisting of aliphatic and carbocyclic aldehydes containing not mor than 8 carbon atoms in monomeric form.

5. The process of treating a cellulose textile material as defined in claim 1 wherein the polymeric acetal condensation product in the bath is a polymeric condensation product of diethylene glycol, glycerine and formaldehyde.

6. The process of treating a cellulose textile material as defined in claim 1 wherein the polymeric acetal condensation product in the bath is a polymeric condensation product of diethylene glycol, pentaerythritol and formaldehyde.

7. Cellulose textile material dimensionally stable to laundering made by the process defined in claim 1.

8. Cellulose textile material dimensionally stable to laundering made by the process defined in claim 3.

9. Cellulose textile material dimensionally stable to laundering made by the process defined in claim 4.

10. Cellulose textile material dimensionally stable to laundering made by the process defined in claim 5.

11. Cellulose textile material dimensionally stable to laundering made by the process defined in claim 6.

References Cited in the file of this patent UNITED STATES PATENTS 2,207,740 'Kaase et a1 July 16, 1940 2,350,350 Gresham June 6, 1944 2,360,477 Dahle Oct. 17, 1944 FOREIGN PATENTS 527,888 Great Britain Oct. 17, 1940 

1. THE PROCESS OF TREATING A CELLULOSE TEXTILE MATERIAL WHICH COMPRISES APPLYING TO A CELLULOSE TEXTILE MATERIAL AN AQUEOUS BATH CONTAINING AN ACIDIC CATALYST AND A POLYMERIC ACETAL CONDENSATION PRODUCT OF A GLYCOL SELECTED FROM THE GROUP CONSISTING OF MONOALKYLENE AND POLYALKYLENE GLYCOLS IN WHICH THE ALKYLENE RADICAL HAS 2 TO 4 CARBON ATOMS IN A STRAIGHT CHAIN AND MIXTURES OF THE AFORESAID GLYCOLS, AND A REACTIVE ALDEHYDE SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC AND CARBOCYCLIC ALDEHYDES CONTAINING NOT MORE THAN 8 CARBON ATOMS IN MONOMERIC FORM AND MIXTURES OF THE AFORESAID ALDEHYDES, SAID CONDENSATION PRODUCT CONTAINING AT LEAST 2 ALDEHYDE UNITS AND AT LEAST 2 POLYHYDRIC ALCOHOL UNITS PER MOLECULE OF CONDENSATION PRODUCT, SAID CATALYST BEING PRESENT IN AMOUNT FROM ABOUT 5% TO ABOUT 200% BY WEIGHT OF THE SAID POLYMERIC CONDENSATION PRODUCT, SAID POLYMERIC CONDENSATION PRODUCT BEING PRESENT IN SAID BATH IN AMOUNT FROM ABOUT 0.5% TO ABOUT 25% BY WEIGHT OF THE BATH AND HEATING THE TREATED TEXTILE MATERIL AT AN ELEVATED TEMPERATURE UNTIL THE CELLULOSE AND SAID POLYMERIC CONDENSATION PRODUCT REACT AND DIMENSIONALLY STABILIZE THE CELLULOSE MATERAL TO LUNDERING. 